Polyisocyanate resins

ABSTRACT

A polyisocyanate resin can include from 25 wt % to 50 wt % of a first cycloaliphatic polyisocyanate and from 50 wt % to 75 wt % of a flexibilizing component based on a total weight of the polyisocyanate resin. The first cycloaliphatic polyisocyanate can have an NCO % of from 12 wt % to 20 wt % based on ISO 11909:2007. The flexibilizing component can include a linear aliphatic polyisocyanate having a number average isocyanate functionality of from 2 to 3 based on gel permeation chromatography and an isocyanate-terminated reaction product of a second cycloaliphatic polyisocyanate and an isocyanate-reactive material, the reaction product having a Tg of less than −30° C. based on a Differential Scanning Calorimetry (2nd Heating) temperature scan from −100° C. to 150° C. using 20° C./min heating and cooling ramps. The isocyanate-terminated reaction product and the linear aliphatic polyisocyanate can be present at a weight ratio of from 0.5 to 2.5.

BACKGROUND

Compositions based on isocyanate chemistry find utility as components incoatings, such as, for example, paints, primers, and the like.Isocyanate-based coating compositions may include, for example,polyurethane or polyurea coatings formed from resins comprisingcomponents, such as, for example, diisocyanates, polyisocyanates,isocyanate reaction products, the like, or a combination thereof. Theseresins may cure by various mechanisms so that covalent bonds formbetween the resin components, thereby producing a cross-linked polymernetwork.

As non-limiting examples, some polyurethane and polyurea coatings can beused to formulate a variety of industrial maintenance and protectivecoatings. Such coatings can be formulated to provide protection tounderlying substrates against corrosion, abrasion, and various otherdegradative stimuli. However, in some cases, as industrial maintenanceand protective coatings age, they can experience changes in performance(e.g., flexibility, weatherability, etc.) and aesthetic appeal (e.g.,color, gloss, etc.). As one example, some industrial maintenance andprotective coatings can undergo color and/or gloss changes in arelatively short period of time. This can present challenges where“touch-up” work may be required because the refinished areas may looknon-uniform as compared to surrounding areas, resulting in anaesthetically undesirable appearance. Thus, in many cases, it can bebeneficial to formulate an industrial maintenance and protective coatingthat has good performance over time, and that also allows foraesthetically acceptable recoatability.

BRIEF SUMMARY

A polyisocyanate resin can include from 25 wt % to 50 wt % of a firstcycloaliphatic polyisocyanate and from 50 wt % to 75 wt % of aflexibilizing component based on a total weight of the polyisocyanateresin. The first cycloaliphatic polyisocyanate can have an NCO % of from12 wt % to 20 wt % based on ISO 11909:2007. The flexibilizing componentcan include an isocyanate-terminated reaction product of a secondcycloaliphatic polyisocyanate and an isocyanate-reactive material, thereaction product having a glass transition temperature (Tg) of less than−30° C. based on a Differential Scanning Calorimetry (2^(nd) Heating)temperature scan from −100° C. to 150° C. using 20° C./min heating andcooling ramps, and a linear aliphatic polyisocyanate having a numberaverage isocyanate functionality of from 2 to 3 based on gel permeationchromatography, wherein the reaction product and the linear aliphaticpolyisocyanate are present at a weight ratio of from 0.5 to 2.5.

A method of manufacturing a polyisocyanate resin can include combining afirst cycloaliphatic polyisocyanate having an NCO % of from 12 wt % to20 wt % based on ISO 11909:2007 and a flexibilizing component at aweight ratio of from 0.3 to 1. The flexibilizing component can include alinear aliphatic polyisocyanate having a number average isocyanatefunctionality of from 2 to 3 based on gel permeation chromatography andan isocyanate-terminated reaction product of a second cycloaliphaticpolyisocyanate and an isocyanate-reactive material. Theisocyanate-terminated reaction product can have a glass transitiontemperature (Tg) of less than −30° C. based on a Differential ScanningCalorimetry (2^(nd) Heating) temperature scan from −100° C. to 150° C.using 20° C./min heating and cooling ramps. The isocyanate-terminatedreaction product and the linear aliphatic polyisocyanate can be combinedat a weight ratio of from 0.5 to 3.f

DETAILED DESCRIPTION

Although the following detailed description contains many specifics forthe purpose of illustration, a person of ordinary skill in the art willappreciate that many variations and alterations to the following detailscan be made and are considered to be included herein. Accordingly, thefollowing embodiments are set forth without any loss of generality to,and without imposing limitations upon, any claims set forth. It is alsoto be understood that the terminology used herein is for the purpose ofdescribing particular embodiments only, and is not intended to belimiting. Unless defined otherwise, all technical and scientific termsused herein have the same meaning as commonly understood by one ofordinary skill in the art to which this disclosure belongs.

As used in this written description, the singular forms “a,” “an” and“the” include express support for plural referents unless the contextclearly dictates otherwise. Thus, for example, reference to “a polymer”or “the polymer” can include a plurality of such polymers.

In this application, “comprises,” “comprising,” “containing” and“having” and the like can have the meaning ascribed to them in U.S.Patent law and can mean “includes,” “including,” and the like, and aregenerally interpreted to be open ended terms. The terms “consisting of”or “consists of” are closed terms, and include only the components,structures, steps, or the like specifically listed in conjunction withsuch terms, as well as that which is in accordance with U.S. Patent law.“Consisting essentially of” or “consists essentially of” have themeaning generally ascribed to them by U.S. Patent law. In particular,such terms are generally closed terms, with the exception of allowinginclusion of additional items, materials, components, steps, orelements, that do not materially affect the basic and novelcharacteristics or function of the item(s) used in connection therewith.For example, trace elements present in a composition, but not affectingthe compositions nature or characteristics would be permissible ifpresent under the “consisting essentially of” language, even though notexpressly recited in a list of items following such terminology. Whenusing an open ended term, like “comprising” or “including,” in thiswritten description it is understood that direct support should beafforded also to “consisting essentially of” language as well as“consisting of” language as if stated explicitly and vice versa.

The terms “first,” “second,” “third,” “fourth,” and the like in thedescription and in the claims, if any, are used for distinguishingbetween similar elements and not necessarily for describing a particularsequential or chronological order. It is to be understood that any termsso used are interchangeable under appropriate circumstances such thatthe embodiments described herein are, for example, capable of operationin sequences other than those illustrated or otherwise described herein.Similarly, if a method is described herein as comprising a series ofsteps, the order of such steps as presented herein is not necessarilythe only order in which such steps may be performed, and certain of thestated steps may possibly be omitted and/or certain other steps notdescribed herein may possibly be added to the method.

As used herein, the term “substantially” refers to the complete ornearly complete extent or degree of an action, characteristic, property,state, structure, item, or result. For example, an object that is“substantially” enclosed would mean that the object is either completelyenclosed or nearly completely enclosed. The exact allowable degree ofdeviation from absolute completeness may in some cases depend on thespecific context. However, generally speaking the nearness of completionwill be so as to have the same overall result as if absolute and totalcompletion were obtained. The use of “substantially” is equallyapplicable when used in a negative connotation to refer to the completeor near complete lack of an action, characteristic, property, state,structure, item, or result. For example, a composition that is“substantially free of” particles would either completely lackparticles, or so nearly completely lack particles that the effect wouldbe the same as if it completely lacked particles. In other words, acomposition that is “substantially free of” an ingredient or element maystill actually contain such item as long as there is no measurableeffect thereof.

As used herein, the term “about” is used to provide flexibility to anumerical range endpoint by providing that a given value may be “alittle above” or “a little below” the endpoint. Unless otherwise stated,use of the term “about” in accordance with a specific number ornumerical range should also be understood to provide support for suchnumerical terms or range without the term “about”. For example, for thesake of convenience and brevity, a numerical range of “about 50milligrams to about 80 milligrams” should also be understood to providesupport for the range of “50 milligrams to 80 milligrams.” Furthermore,it is to be understood that in this specification support for actualnumerical values is provided even when the term “about” is usedtherewith. For example, the recitation of “about” 30 should be construedas not only providing support for values a little above and a littlebelow 30, but also for the actual numerical value of 30 as well. Unlessotherwise specified, all numerical parameters are to be understood asbeing prefaced and modified in all instances by the term “about,” inwhich the numerical parameters possess the inherent variabilitycharacteristic of the underlying measurement techniques used todetermine the numerical value of the parameter.

As used herein, a plurality of items, structural elements, compositionalelements, and/or materials may be presented in a common list forconvenience. However, these lists should be construed as though eachmember of the list is individually identified as a separate and uniquemember. Thus, no individual member of such list should be construed as ade facto equivalent of any other member of the same list solely based ontheir presentation in a common group without indications to thecontrary.

Concentrations, amounts, and other numerical data may be expressed orpresented herein in a range format. It is to be understood that such arange format is used merely for convenience and brevity and thus shouldbe interpreted flexibly to include not only the numerical valuesexplicitly recited as the limits of the range, but also to include allthe individual numerical values or sub-ranges encompassed within thatrange as if each numerical value and sub-range is explicitly recited. Asan illustration, a numerical range of “1 to 5” should be interpreted toinclude not only the explicitly recited values of 1 to 5, but alsoinclude individual values and sub-ranges within the indicated range.Thus, included in this numerical range are individual values such as 2,3, and 4 and sub-ranges such as from 1-3, from 2-4, and from 3-5, etc.,as well as 1, 2, 3, 4, and 5, individually.

This same principle applies to ranges reciting only one numerical valueas a minimum or a maximum. Furthermore, such an interpretation shouldapply regardless of the breadth of the range or the characteristicsbeing described.

Reference throughout this specification to “an example” means that aparticular feature, structure, or characteristic described in connectionwith the example is included in at least one embodiment. Thus,appearances of the phrases “in an example” in various places throughoutthis specification are not necessarily all referring to the sameembodiment.

Corrosion-resistant coatings have found use on a number ofinfrastructure assets, such as bridges and municipal sports stadiums.However, some corrosion-resistant coatings have one or more challengesthat limit their usefulness. For example, some corrosion-resistantcoatings may not recoat well, resulting in recoated layers that do notadhere well to the underlying coating and easily peel off. In othercases, corrosion-resistant coatings may suffer from gloss loss overrelatively short periods of time, resulting in patchy touch-up work thatis not aesthetically desirable. In still additional cases, somecorrosion-resistant coatings may have suitable performance for someinfrastructure assets, but lack the flexibility for other markets thatdemand more flexible coatings.

The present disclosure describes polyisocyanate resins that can be usedto formulate a coating composition having good recoatability and thatprovides a coating having low gloss loss and good flexibility.Specifically, the present disclosure describes a polyisocyanate resinincluding a first cycloaliphatic polyisocyanate combined with aflexibilizing component.

In further detail, the polyisocyanate resin described herein can includeor be formed from a first cycloaliphatic polyisocyanate. Without wishingto be bound by theory, it is believed that incorporating acycloaliphatic polyisocyanate into a polyisocyanate resin can impartgood gloss stability to the resin. Thus, the polyisocyanate resindescribed herein can generally include at least 25 wt % of a firstcycloaliphatic polyisocyanate to help maintain good gloss stability. Insome additional examples, the first cycloaliphatic polyisocyanate can beincluded in a polyisocyanate resin in an amount of from 25 wt % to 50 wt% based on a total weight of the resin. In some specific examples, thefirst cycloaliphatic polyisocyanate can be included in a polyisocyanateresin in an amount of from 25 wt % to 35 wt %, or from 35 wt % to 45 wt% based on a total weight of the resin. In some additional specificexamples, the first cycloaliphatic polyisocyanate can be included in apolyisocyanate resin in an amount of from 30 wt % to 40 wt %, or from 40wt % to 50 wt % based on a total weight of the resin.

As used herein, the term “polyisocyanate” refers to compounds comprisingat least two un-reacted isocyanate groups. The term “diisocyanate”refers to compounds having two un-reacted isocyanate groups. Thus,“diisocyanate” is a subset of “polyisocyanate.” Polyisocyanates caninclude biurets, isocyanurates, uretdiones, isocyanate-functionalurethanes, isocyanate-functional ureas, isocyanate-functionaliminooxadiazine diones, isocyanate-functional oxadiazine diones,isocyanate-functional carbodiimides, isocyanate-functional acyl ureas,isocyanate-functional allophanates, the like, or combinations thereof.

As non-limiting examples, isocyanurates may be prepared by the cyclictrimerization of polyisocyanates. Trimerization may be performed, forexample, by reacting three (3) equivalents of a polyisocyanate toproduce 1 equivalent of isocyanurate ring. The three (3) equivalents ofpolyisocyanate may comprise three (3) equivalents of the samepolyisocyanate compound, or various mixtures of two (2) or three (3)different polyisocyanate compounds. Compounds, such as, for example,phosphines, Mannich bases and tertiary amines, such as, for example,1,4-diaza-bicyclo[2.2.2]octane, dialkyl piperazines, or the like, may beused as trimerization catalysts. Iminooxadiazines may be prepared by theasymmetric cyclic trimerization of polyisocyanates. Uretdiones may beprepared by the dimerization of a polyisocyanate. Allophanates may beprepared by the reaction of a polyisocyanate with a urethane. Biuretsmay be prepared via the addition of a small amount of water to twoequivalents of polyisocyanate and reacting at slightly elevatedtemperature in the presence of a biuret catalyst. Biurets may also beprepared by the reaction of a polyisocyanate with a urea.

With this in mind, the first cycloaliphatic polyisocyanate can includeor be formed from a variety of cycloaliphatic polyisocyanates.Non-limiting examples can include1-isocyanato-3,3,5-trimethyl-5-isocyanato-methylcyclohexane (IPDI),2,4-diisocyanato-dicyclohexyl-methane, 4,4′diisocyanato-dicyclohexyl-methane,1-isocyanato-1-methyl-3(4)-isocyanatomethyl-cyclohexane (IMCI),1,4-cyclohexane diisocyanate (CHDI), the like, or a combination thereof.In some specific examples, the first cycloaliphatic polyisocyanate caninclude a secondary isocyanate group. By “secondary isocyanate group,”it is meant an isocyanate group bonded to a secondary carbon atom.

In some further examples, the first cycloaliphatic polyisocyanate can beor include a biuret, a trimer, an allophanate, the like, or acombination thereof. For example, in some cases, the firstcycloaliphatic polyisocyanate can be or include a trimer, such as atrimer of IPDI, a trimer of 2,4-diisocyanato-dicyclohexyl-methane, atrimer of 4,4′ diisocyanato-dicyclohexyl-methane, a trimer of IMCI, atrimer of CHDI, or a combination thereof. In other examples, the firstcycloaliphatic polyisocyanate can be or include a biuret, such as abiuret of IPDI, a biuret of 2,4-diisocyanato-dicyclohexyl-methane, abiuret of 4,4′ diisocyanato-dicyclohexyl-methane, a biuret of IMCI, abiuret of CHDI, or a combination thereof. In still additional examples,the first cycloaliphatic polyisocyanate can be or include anallophanate, such as an allophanate of IPDI, an allophanate of2,4-diisocyanato-dicyclohexyl-methane, an allophanate of 4,4′diisocyanato-dicyclohexyl-methane, an allophanate of IMCI, anallophanate of CHDI, or a combination thereof.

In some specific examples, the first cycloaliphatic polyisocyanate canbe or include an IPDI polyisocyanate. Where this is the case, in someexamples, the IPDI polyisocyanate can be or include an IPDI trimer, anIPDI allophanate, or a combination thereof. In some additional examples,the IPDI polyisocyanate can include an allophanate of an IPDI trimer. Insome other examples, the IPDI polyisocyanate can include an IPDI trimer,but not an allophanate.

The first cycloaliphatic polyisocyanate can generally have an NCO % offrom 12 wt % to 20 wt % based on ISO 11909:2007. In some additionalexamples, the first cycloaliphatic polyisocyanate can have an NCO % offrom 12 wt % to 16 wt %, from 14 wt % to 18 wt %, or from 16 wt % to 20wt % based on ISO 11909:2007.

In some examples, the first cycloaliphatic polyisocyanate can have anumber average isocyanate functionality of from 2.4 to 3.8 based on gelpermeation chromatography using polystyrene standards. In someadditional examples, the first cycloaliphatic polyisocyanate can have anumber average isocyanate functionality of from 2.4 to 3.0, from 2.8 to3.4, or from 3.2 to 3.8 based on gel permeation chromatography usingpolystyrene standards.

While the first cycloaliphatic polyisocyanate may provide good glossstability to the polyisocyanate resin, the resin may still lacksufficient flexibility for some applications without the addition of aflexibilizing component. Thus, in addition to the first cycloaliphaticpolyisocyanate, the polyisocyanate resin described herein can alsoinclude a flexibilizing component. Generally, a flexibilizing componentis included in the polyisocyanate resin in an amount of at least 50 wt %based on a total weight of the polyisocyanate resin. In some examples, aflexibilizing component can be included in the polyisocyanate resin inan amount of from 50 wt % to 75 wt % based on a total weight of thepolyisocyanate resin. In some specific examples, the flexibilizingcomponent can be included in the polyisocyanate resin in an amount offrom 50 wt % to 60 wt %, from 55 wt % to 65 wt %, from 60 wt % to 70 wt%, or from 65 wt % to 75 wt % based on a total weight of thepolyisocyanate resin.

In further detail, the flexibilizing component can include one or morepolyisocyanate components that are suitable to increase the deformationresistance of the polyisocyanate resin, while helping to maintain goodgloss stability. As such, the flexibilizing component can generallyinclude one or more materials having a relatively low glass transitiontemperature (Tg).

In some examples, the flexibilizing component can be or include anisocyanate-terminated reaction product of a second cycloaliphaticpolyisocyanate with an isocyanate-reactive material. The secondcycloaliphatic polyisocyanate can independently be or include acycloaliphatic aliphatic polyisocyanate described with respect to thefirst cycloaliphatic polyisocyanate. More specifically, the secondcycloaliphatic polyisocyanate can include a variety of cycloaliphaticpolyisocyanates. Non-limiting examples can include1-isocyanato-3,3,5-trimethyl-5-isocyanato-methylcyclohexane (IPDI),2,4-diisocyanato-dicyclohexyl-methane, 4,4′diisocyanato-dicyclohexyl-methane,1-isocyanato-1-methyl-3(4)-isocyanatomethyl-cyclohexane (IMCI),1,4-cyclohexane diisocyanate (CHDI), the like, or a combination thereof.In some specific examples, the second cycloaliphatic polyisocyanate caninclude a secondary isocyanate group. By “secondary isocyanate group,”it is meant an isocyanate group bonded to a secondary carbon atom.

In some further examples, the second cycloaliphatic polyisocyanate canbe or include a biuret, a trimer, an allophanate, the like, or acombination thereof. For example, in some cases, the secondcycloaliphatic polyisocyanate can be or include a trimer, such as atrimer of IPDI, a trimer of 2,4-diisocyanato-dicyclohexyl-methane, atrimer of 4,4′ diisocyanato-dicyclohexyl-methane, a trimer of IMCI, atrimer of CHDI, or a combination thereof. In other examples, the secondcycloaliphatic polyisocyanate can be or include a biuret, such as abiuret of IPDI, a biuret of 2,4-diisocyanato-dicyclohexyl-methane, abiuret of 4,4′ diisocyanato-dicyclohexyl-methane, a biuret of IMCI, abiuret of CHDI, or a combination thereof. In still additional examples,the second cycloaliphatic polyisocyanate can be or include anallophanate, such as an allophanate of IPDI, an allophanate of2,4-diisocyanato-dicyclohexyl-methane, an allophanate of 4,4′diisocyanato-dicyclohexyl-methane, an allophanate of IMCI, anallophanate of CHDI, or a combination thereof.

In some specific examples, the second cycloaliphatic polyisocyanate canbe or include an IPDI polyisocyanate. Where this is the case, in someexamples, the IPDI polyisocyanate can be or include an IPDI trimer, anIPDI allophanate, or a combination thereof. In some additional examples,the IPDI polyisocyanate can include an allophanate of an IPDI trimer. Insome other examples, the IPDI polyisocyanate can include an IPDI trimer,but not an allophanate.

In some examples, the second cycloaliphatic polyisocyanate can be orinclude the same cycloaliphatic polyisocyanate as the firstcycloaliphatic polyisocyanate. In other examples, the secondcycloaliphatic polyisocyanate can be or include a differentcycloaliphatic polyisocyanate from the first cycloaliphaticpolyisocyanate.

A variety of isocyanate-reactive materials can be combined with thesecond cycloaliphatic polyisocyanate and allowed to react to produce theisocyanate-terminated reaction product. For example, theisocyanate-reactive material can generally include a polyol or polyaminethat is based on a polyether, a polyester, a polycarbonate, apolycarbonate ester, a polycaprolactone, a polybutadiene, the like, or acombination thereof. In some specific examples, the isocyanate-reactivematerial can include a polyether polyol. In some additional specificexamples, the isocyanate-reactive material can include a polyesterpolyol. Additionally, the isocyanate-reactive material can generallyhave a number average molecular weight of from 300 g/mol to 6000 g/mol.

Examples of polyether polyols can be formed from the oxyalkylation ofvarious polyols, for example, glycols such as ethylene glycol, 1,2- 1,3-or 1,4-butanediol, 1,6-hexanediol, and the like, or higher polyols, suchas trimethylol propane, pentaerythritol and the like. One commonlyutilized oxyalkylation method is by reacting a polyol with an alkyleneoxide, for example, ethylene oxide or propylene oxide in the presence ofa basic catalyst or a coordination catalyst such as a double-metalcyanide (DMC).

Examples of suitable polyester polyols can be prepared by thepolyesterification of organic polycarboxylic acids, anhydrides thereof,or esters thereof with organic polyols. Preferably, the polycarboxylicacids and polyols are aliphatic or aromatic dibasic acids and diols.

The diols which may be employed in making the polyester include alkyleneglycols, such as ethylene glycol, 1,2- 1,3- or 1,4-butanediol, neopentylglycol and other glycols such as cyclohexane dimethanol, caprolactonediol (for example, the reaction product of caprolactone and ethyleneglycol), polyether glycols, for example, poly(oxytetramethylene) glycoland the like. However, other diols of various types and, as indicated,polyols of higher functionality may also be utilized in variousembodiments of the invention. Such higher polyols can include, forexample, trimethylol propane, trimethylol ethane, pentaerythritol, andthe like, as well as higher molecular weight polyols such as thoseproduced by oxyalkylating low molecular weight polyols.

The acid component of the polyester can include primarily monomericcarboxylic acids, or anhydrides thereof, or esters thereof having 2 to18 carbon atoms per molecule. Among the acids that are useful arephthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalicacid, hexahydrophthalic acid, adipic acid, succinic acid, azelaic acid,sebacic acid, maleic acid, glutaric acid, chlorendic acid,tetrachlorophthalic acid and other dicarboxylic acids of varying types.Also, there may be employed higher polycarboxylic acids such astrimellitic acid and tricarballylic acid.

In addition to polyester polyols formed from polybasic acids andpolyols, polycaprolactone-type polyesters can also be employed. Theseproducts are formed from the reaction of a cyclic lactone such asε-caprolactone with a polyol containing primary hydroxyls such as thosementioned above. Such products are described in U.S. Pat. No. 3,169,949,which is incorporated herein by reference.

Suitable hydroxy-functional polycarbonate polyols may be those preparedby reacting monomeric diols (such as 1,4-butanediol, 1,6-hexanediol,di-, tri- or tetraethylene glycol, di-, tri- or tetrapropylene glycol,3-methyl-1,5-pentanediol, 4,4′-dimethylolcyclohexane and mixturesthereof) with diaryl carbonates (such as diphenyl carbonate, dialkylcarbonates (such as dimethyl carbonate and diethyl carbonate), alkylenecarbonates (such as ethylene carbonate or propylene carbonate), orphosgene. Optionally, a minor amount of higher functional, monomericpolyols, such as trimethylolpropane, glycerol or pentaerythritol, may beused.

In other examples, low molecular weight diols, triols, and higheralcohols may be included in the isocyanate-reactive material. In manyembodiments, they can be monomeric and have hydroxyl values of 375 to1810. Such materials can include aliphatic polyols, particularlyalkylene polyols containing from 2 to 18 carbon atoms. Examples includeethylene glycol, 1,4-butanediol, 1,6-hexanediol, and cycloaliphaticpolyols such as cyclohexane dimethanol. Examples of triols and higheralcohols include trimethylol propane and pentaerythritol. Also usefulare polyols containing ether linkages such as diethylene glycol andtriethylene glycol.

Thus, the isocyanate-terminated reaction product can be prepared from avariety of materials. Additionally, the isocyanate-terminated reactionproduct can generally have a Tg of less than −30° C. based on aDifferential Scanning Calorimetry reheat (2^(nd) Heating) from −100° C.to 150° C. using 20° C./min heating and cooling ramps. In stilladditional examples, the isocyanate-terminated reaction product can havea Tg of less than −35° C., less than −40° C., or less than −45° C. basedon a Differential Scanning Calorimetry reheat (2^(nd) Heating) from−100° C. to 150° C. using 20° C./min heating and cooling ramps.

The isocyanate-terminated reaction product can also generally have anumber average isocyanate functionality of from 1.8 to 2.8 based on gelpermeation chromatography using polystyrene standards. In someadditional examples, the isocyanate-terminated reaction product can havea number average isocyanate functionality of from 1.8 to 2.2, from 2.0to 2.4, from 2.2 to 2.6, or from 2.4 to 2.8 based on gel permeationchromatography using polystyrene standards.

In still additional examples, the isocyanate-terminated reaction productcan have a variety of NCO contents. In some examples, theisocyanate-terminated reaction product can have an NCO % of from 2 wt %to 14 wt % based on ISO 11909:2007. In other examples, theisocyanate-terminated reaction product can have an NCO % of from 2 wt %to 6 wt %, from 4 wt % to 10 wt %, or from 8 wt % to 14 wt % based onISO 11909:2007. In some specific examples, the isocyanate-terminatedreaction product can have an NCO % of from 2.5 wt % to 4 wt % based onISO 11909:2007.

In some additional examples, the flexibilizing component can alsoinclude a linear aliphatic polyisocyanate. As used herein, “linearaliphatic polyisocyanate” refers to a polyisocyanate that is preparedfrom or based on a linear isocyanate monomer, such as 1,4-tetramethylenediisocyanate, 1,5-pentamethylene diisocyanate, or 1,6-hexamethylenediisocyanate. Thus, for example, while the structure of a trimer of1,6-hexamethylene diisocyanate may not be entirely linear, it is basedon the linear monomeric 1,6-hexamethylene diisocyanate and is thereforeconsidered a “linear aliphatic polyisocyanate” for the purposes of thisdisclosure. Non-limiting examples of linear aliphatic polyisocyanatescan include 1,4-tetramethylene diisocyanate, 1,5-pentamethylenediisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), a trimer ofHDI, a trimer of PDI, a biuret of HDI, a biuret of PDI, an allophanateof HDI, an allophanate of PDI, an allophanate of a trimer of HDI, anallophanate of a trimer of PDI, 2,2,4-trimethyl-hexamethylenediisocyanate, 2,4,4-trimethyl-hexamethylene diisocyanate,dodecamethylene diisocyanate, 2-methyl-1,5-diisocyanatopentane, thelike, or a combination thereof.

In some specific examples, the linear aliphatic polyisocyanate can be orinclude an HDI polyisocyanate. In some additional specific examples, thelinear aliphatic polyisocyanate can be or include a PDI polyisocyanate.In some specific examples, the linear aliphatic polyisocyanate can be orinclude a biuret, such as a biuret of HDI, a biuret of PDI, or acombination thereof. In some additional specific examples, the linearaliphatic polyisocyanate can be or include a trimer, such as a trimer ofHDI, a trimer of PDI, or a combination thereof. In still furtherspecific examples, the linear aliphatic polyisocyanate can be or includean allophanate, such as an allophanate of HDI, an allophanate of PDI, anallophanate of a trimer of HDI, an allophanate of a trimer of PDI, or acombination thereof.

The linear aliphatic polyisocyanate can generally have a relatively lownumber average isocyanate functionality to reduce the crosslinkingdensity and provide a resin with greater flexibility. In some examples,the linear aliphatic polyisocyanate can have a number average isocyanatefunctionality of from 2 to 3 based on gel permeation chromatography withpolystyrene standards. In some specific examples, the linear aliphaticpolyisocyanate can have a number average isocyanate functionality offrom 2.0 to 2.5, from 2.3 to 2.8, or from 2.5 to 3.0 based on gelpermeation chromatography using polystyrene standards.

In some examples, the linear aliphatic polyisocyanate can have an NCO %of from 15 wt % to 25 wt % based on ISO 11909:2007. In some specificexamples, the linear aliphatic polyisocyanate can have an NCO % of from15 wt % to 20 wt %, from 18 wt % to 22 wt %, or from 20 wt % to 25 wt %based on ISO 11909:2007.

In some examples, the flexibilizing component can include theisocyanate-terminated reaction product. In some additional examples, theflexibilizing component can include the linear aliphatic polyisocyanate.In still additional examples, the flexibilizing component can includeboth the isocyanate-terminated reaction product and the linear aliphaticpolyisocyanate.

Where the flexibilizing component includes both theisocyanate-terminated reaction product and the linear aliphaticpolyisocyanate, the isocyanate-terminated reaction product and thelinear aliphatic polyisocyanate are generally included at a weight ratioof from 0.5 to 3.0 reaction product/linear aliphatic polyisocyanate. Inother examples, the isocyanate-terminated reaction product and thelinear aliphatic polyisocyanate can be included in the polyisocyanateresin at a weight ratio of from 0.5 to 1.5, from 1.0 to 2.0, from 1.5 to2.5, or from 2.0 to 3.0.

Thus, the polyisocyanate resin can include a variety of aliphaticpolyisocyanates. Generally, the polyisocyanate resin does not include anaromatic polyisocyanate. In some examples, the polyisocyanate resinincludes less than 5 wt %, less than 1 wt %, less than 0.1 wt %, or lessthan 0.01 wt % of an aromatic polyisocyanate.

In some examples, the polyisocyanate resin is not diluted in a solventand has 100 wt % solids based on a total weight of the polyisocyanateresin. In some other examples, the polyisocyanate resin can be dilutedin a solvent to form a polyisocyanate composition. A variety of solventscan be used to dilute the polyisocyanate resin and reduce the viscositythereof. Non-limiting examples of solvents that can be employed in thepolyisocyanate composition can include ethyl acetate, butyl acetate,1-methoxy propyl-acetate-2, acetone, methyl ethyl ketone, methylisobutyl ketone, cyclohexanone, toluene, xylene, solvent naphtha, thelike, or a combination thereof. In some specific examples, the solventcan include butyl acetate, methyl ethyl ketone, methoxypropylacetate, ora combination thereof.

In some examples, the polyisocyanate resin can be diluted in solvent toprepare a polyisocyanate composition having a solids content of from 80wt % solids to 99 wt % solids based on a total weight of thepolyisocyanate composition. In other examples, the polyisocyanate resincan be diluted in solve to prepare a polyisocyanate composition having asolids content of from 85 wt % to 95 wt %, from 86 wt % to 94 wt %, orfrom 87 wt % to 93 wt % based on a total weight of the polyisocyanatecomposition.

In some examples, the polyisocyanate resin or polyisocyanate compositioncan have a viscosity of from 500 mPas to 1300 MPas at 25° C. based onISO 3219/A.3. In some additional examples, the polyisocyanate resin orpolyisocyanate composition can have a viscosity of from 600 mPas to 1200MPas, or from 700 mPas to 1100 MPas at 25° C. based on ISO 3219/A.3.

In some additional examples, the polyisocyanate resin or polyisocyanatecomposition can have an NCO % of from 8 wt % to 16 wt % based on ISO11909:2007. In other examples, the polyisocyanate resin can have an NCO% of from 8 wt % to 12 wt %, from 10 wt % to 14 wt % or from 12 wt % to16 wt % based on ISO 11909:2007.

In still additional examples, the polyisocyanate resin or polyisocyanatecomposition can include less than 1 wt % polyisocyanate monomer based ona total weight of the polyisocyanate resin or polyisocyanatecomposition. In still additional examples, the polyisocyanate resin orpolyisocyanate composition can include less than 0.8 wt %, less than 0.7wt %, or less than 0.6 wt % polyisocyanate monomer based on a totalweight of the polyisocyanate resin or polyisocyanate composition.

The present disclosure also describes methods of manufacturingpolyisocyanate resins. The methods can include combining a firstcycloaliphatic polyisocyanate as described herein and a flexibilizingcomponent as described herein at a weight ratio of from 0.3 to 1 firstcycloaliphatic polyisocyanate/flexibilizing component. In someadditional examples, the first cycloaliphatic polyisocyanate and theflexibilizing component can be combined at a weight ratio of from 0.3 to0.7, from 0.4 to 0.8, from 0.5 to 0.9, or from 0.6 to 1 firstcycloaliphatic polyisocyanate/flexibilizing component.

In some specific examples, the first cycloaliphatic polyisocyanate canhave an NCO % of from 12 wt % to 20 wt % based on ISO 11909:2007. Inadditional specific examples, the flexibilizing component can include anisocyanate-terminated reaction product of a second cycloaliphaticpolyisocyanate and an isocyanate reactive material as well as a linearaliphatic polyisocyanate. Where this is the case, theisocyanate-terminated reaction product and the linear aliphaticpolyisocyanate can be combined at a weight ratio of from 0.5 to 2.5.

Combining the first cycloaliphatic polyisocyanate and the flexibilizingcomponent can be performed in a variety of ways. In some examples, thefirst cycloaliphatic polyisocyanate and the flexibilizing component canbe combined by reacting individual components to form anisocyanate-terminated prepolymer. In other examples, the firstcycloaliphatic polyisocyanate and the flexibilizing component may becombined by mixing to form a blend.

Similarly, in some examples, combining individual constituents of theflexibilizing component can be performed by reacting the individualcomponents together to form a prepolymer. In other examples, individualconstituents of the flexibilizing component may be combined by mixing toform a blend.

In some additional examples, a solvent can be used to dilute the resinor one or more individual resin components to reduce the viscositythereof to facilitate the reaction and/or mixing process. A variety ofsolvents, such as those described elsewhere herein, can be used asdiluents. In other examples, one or more constituents of thepolyisocyanate resin can have a sufficiently low viscosity to act as areactive diluent without using any additional diluents.

The polyisocyanate resin described herein, or the polyisocyanatecomposition where diluted with a solvent, can be part of a two-component(2K) polyurea or polyurethane coating system. Thus, the presentdisclosure also describes a 2K coating system including a polyisocyanateresin as described herein, or polyisocyanate composition, and apolyapartate composition or other isocyanate-reactive composition. Thepresent disclosure also describes a polyurea or polyurethane coatingcomposition including a mixture and/or reaction product of thepolyisocyanate resin as described herein and a polyaspartate compositionor other isocyanate-reactive composition at an equivalent ratio of from1:1 to 1.2:1 NCO:NH or NCO:OH. In some additional examples, thepolyisocyanate composition can be combined with the polyaspartatecomposition or other isocyanate-reactive composition at an equivalentratio of from 1:1 to 1.06:1, from 1.04:1 to 1.1:1, or from 1.1:1 to1.2:1 NCO:NH or NCO:OH.

In some specific examples, the polyisocyanate resin can be combined witha polyaspartate composition to produce a coating composition. In furtherdetail, polyaspartates may be produced by the reaction of a polyaminewith a Michael addition receptor, i.e., an olefin substituted on one orboth of the olefinic carbons with an electron withdrawing group such ascyano, keto or ester (an electrophile) in a Michael addition reaction.Examples of suitable Michael addition receptors include, but are notlimited to, acrylates, and diesters such as dimethyl maleate, diethylmaleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, anddibutyl fumarate.

Additionally, the polyaspartate can be prepared with a variety ofpolyamines, including low molecular weight diamines, high molecularweight diamines, or a combination thereof. Additionally, the polyaminescan have a wide range of amine functionality, repeat unit type,distribution, etc. This wide range of molecular weight, aminefunctionality, repeating unit type, and distribution can provideversatility in the design of new compounds or mixtures.

Suitable low molecular weight diamines have molecular weights in variousembodiments of from 60 to 400, in selected embodiments of from 60 to300. Suitable low-molecular-weight diamines include, but are not limitedto, ethylene diamine, 1,2- and 1,3-diaminopropane, 1,5-diaminopentane,1,3-, 1,4- and 1,6-diaminohexane, 1,3-diamino-2,2-dimethyl propane,2-methylpentamethylenediamine, isophorone diamine,4,4′-diamino-dicyclohexyl methane, 4,4-diamino-3,3′-dimethyldicyclohexylmethane, 1,4-bis(2-amino-prop-2-yl)-cyclohexane, hydrazine, piperazine,bis(4-aminocyclohexyl)methane, and and mixtures of such diamines.Representative polyaspartates prepared from these low molecular weightdiamines include DESMOPHEN NH-1220, DESMOPHEN NH-1420, and DESMOPHENNH-1520, commercially available from COVESTRO.

In some additional embodiments of the invention, a single high molecularweight polyamine may be used. Also, mixtures of high molecular weightpolyamines, such as mixtures of di- and trifunctional materials and/ordifferent molecular weight or different chemical composition materials,may be used. The term “high molecular weight” is intended to includepolyamines having a molecular weight of at least 400 in variousembodiments. In selected embodiments, the polyamines have a molecularweight of from 400 to 6,000. Non-limiting examples can includepolyethylene glycol bis(amine), polypropylene glycol bis(2-aminopropylether), the like, or a combination thereof.

In some specific examples, the polyamine can be an amine-terminatedpolyether. Commercially available examples of amine-terminatedpolyethers include, for example, the JEFFAMINE series ofamine-terminated polyethers from Huntsman Corp., such as, JEFFAMINED-230, JEFFAMINE D-400, JEFFAMINE D-2000, JEFFAMINE D-4000, JEFFAMINET-3000 and JEFFAMINE T-5000.

In some examples, the polyaspartate may include one or morepolyaspartates corresponding to formula (I):

wherein:n is an integer of at least 2;X represents an aliphatic residue;R₁ and R₂ independently of each other represent organic groups that areinert to isocyanate groups under reaction conditions; and

R₃ and R₄ independently of each other represent hydrogen or organicgroups that are inert to isocyanate groups under reaction conditions.

In some additional examples, n has a value of from 2 to 6. In stilladditional examples, n has a value of from 2 to 4. In still additionalexamples, n has a value of 2.

In some examples, X represents an organic group that has a valency of nand is inert towards isocyanate groups at a temperature of 100° C. orless. In some additional examples, X represents a group obtained byremoving amino groups from an aliphatic, araliphatic, or cycloaliphaticpolyamine.

In some examples, R₁ and R₂ independently represent an alkyl grouphaving from 1 to 9 carbon atoms. In some specific examples, R₁ and R₂independently represent a methyl, ethyl, or butyl group. In stilladditional examples, R₁ and R₂, together form a cycloaliphatic orheterocyclic ring.

Other isocyanate-reactive compositions can also be combined with thepolyisocyanate resins described herein. Other isocyanate-reactivecompositions can generally include a polyol or a polyamine that is basedon a polyether, a polyester, a polycarbonate, a polycarbonate ester, apolycaprolactone, a polybutadiene, the like, or a combination thereof,such as those described elsewhere herein. In some further examples, theisocyanate-reactive composition can include such a polyol or polyaminehaving a number average molecular weight of from 300 g/mol to 10,000g/mol, from 400 g/mol to 6000 g/mol, or from 600 g/mol to 4000 g/mol.

It is further noted that the polyisocyanate resin or composition, thepolyaspartate composition, the other isocyanate-reactive composition, ora combination thereof can optionally include one or more additives.Non-limiting examples of additives can include a dispersant, a flow aid,a surfactant, a thickener, a colorant, a solvent, a leveling agent, thelike, or a combination thereof.

Thus, the polyisocyanate resin or composition can be combined with apolyaspartate composition or other isocyanate-reactive composition toform a coating composition. The coating composition can be coated on asurface portion of a variety of substrates. Non-limiting examples ofsubstrates can include metals, plastics, wood, cement, concrete, glass,the like, or a combination thereof.

In further detail, the coating composition can be applied by spraying,knife coating, curtain coating, vacuum coating, rolling, pouring,dipping, spin coating, squeegeeing, brushing, squirting, printing, thelike, or a combination thereof. Printing techniques can include screen,gravure, flexographic, or offset printing and also various transfermethods.

The coating composition can be applied to a portion of a substrate at avariety of coating thicknesses (e.g., wet film thicknesses). Forexample, in some cases, the coating composition can be applied to asurface portion of a substrate at a coating thickness of from 1thousandth of an inch (mil) to 16 mils. In other examples, the coatingcomposition can be applied to a surface portion of a substrate at acoating thickness of from 1 mil to 5 mils, from 3 mils to 9 mils, from 6mils to 12 mils, or from 10 mils to 16 mils.

In some specific examples, the coating composition can be coated on asurface portion of a substrate and cured to form a polyurea coating. Insome examples, the polyurea coating can have relatively stable glossvalues over a period of at least 4 weeks. For example, in some cases,the polyurea coating can have a change in 60° gloss values of less thanor equal to 9 gloss units from 4 hours to 4 weeks after applying thecoating composition to the surface portion based on ASTM D523 andstorage conditions of 75° F. and relative humidity of 55%. In someadditional examples, the polyurea coating can have a change in 60° glossvalues of less than or equal to 7, 6, or 5 gloss units from 4 hours to 4weeks after applying the coating composition to the surface portionbased on ASTM D523 and storage conditions of 75° F. and relativehumidity of 55%.

In some additional examples, the polyurea coating can have a change in60° gloss values of less than or equal to 20 gloss units from 1 hour to4 weeks after applying the coating composition to the surface portionbased on ASTM D523 and initial storage conditions of 120° F. andrelative humidity of 80% for a period of 30 minutes followed bysubsequent storage conditions of 104° F. and relative humidity of 80%for a remainder of the 4 week testing period. In still additionalexamples, the polyurea coating can have a change in 60° gloss values ofless than or equal to 15, 12, or 7 gloss units from 1 hour to 4 weeksafter applying the coating composition to the surface portion based onASTM D523 and initial storage conditions of 120° F. and relativehumidity of 80% for a period of 30 minutes followed by subsequentstorage conditions of 104° F. and relative humidity of 80% for aremainder of the 4 week testing period.

Additionally, in some examples, the polyurea coating can havedeformation resistance of at least 30 inch-pounds (in-lbs) 4 weeks afterapplying the coating composition to the surface portion based on ASTMD523 and initial storage conditions of 120° F. and relative humidity of80% for a period of 30 minutes followed by subsequent storage conditionsof 104° F. and relative humidity of 80% for a remainder of the 4 weektesting period. In some further examples, the polyurea coating can havedeformation resistance of at least 35, 40, or 45 inch-pounds (in-lbs) 4weeks after applying the coating composition to the surface portionbased on ASTM D523 and initial storage conditions of 120° F. andrelative humidity of 80% for a period of 30 minutes followed bysubsequent storage conditions of 104° F. and relative humidity of 80%for a remainder of the 4 week testing period.

EXAMPLES

Materials used in the examples:

-   Polyaspartate A a 100% solids content aspartic ester functional    amine, having an amine number of 200 mg KOH/g, viscosity @ 25° C. of    1100-1500 mPa·s.-   Polyaspartate B a 100% solids content aspartic ester functional    amine, having an amine number of 190 mg KOH/g, viscosity @ 25° C. of    1000-1800 mPa·s.-   Polyisocyanate A a cycloaliphatic polyisocyanate based on IPDI and    having an NCO % of from 10%-11% based on ISO 11909:2007 and a number    average isocyanate functionality of from 2.4-3.0 based on gel    permeation chromatography.-   Polyisocyanate B a cycloaliphatic polyisocyanate based on IPDI    having an NCO % of from 10%-11% based on ISO 11909:2007 and a number    average isocyanate functionality of from 3.3-3.8 based on gel    permeation chromatography.-   Polyisocyanate C an aliphatic polyisocyanate based on HDI and having    an NCO % of from 10%-12% based on ISO 11909:2007, a number average    isocyanate functionality of from 3.5-4.0 based on gel permeation    chromatography, and a Tg of −2° C. based on a Differential Scanning    Calorimetry reheat (2^(nd) Heating) from −100° C. to 150° C. using    20° C./min heating and cooling ramps.-   Polyisocyanate D an aliphatic polyisocyanate based on a reaction    product of HDI and a polyether polyol having an NCO % of 6% based on    ISO 11909:2007, a number average functionality of 4 based on gel    permeation chromatography, and a Tg of −53° C. based on a    Differential Scanning Calorimetry reheat (2^(nd) Heating) from    −100° C. to 150° C. using 20° C./min heating and cooling ramps.-   Polyisocyanate E a reaction product of a cycloaliphatic    polyisocyanate based on IPDI and a polycarbonate polyol having an    NCO % of from 2%-5% based on ISO 11909:2007, a number average    functionality of 2 based on gel permeation chromatography, and a Tg    of −45° C. based on a Differential Scanning Calorimetry reheat    (2^(nd) Heating) from −100° C. to 150° C. using 20° C./min heating    and cooling ramps.-   Polyisocyanate F is a reaction product of a cycloaliphatic    polyisocyanate based on IPDI and a polyether polyol having an NCO %    of from 2%-5% based on ISO 11909:2007, a number average    functionality of 2 based on gel permeation chromatography, and a Tg    of −50° C. based on a Differential Scanning Calorimetry reheat    (2^(nd) Heating) from −100° C. to 150° C. using 20° C./min heating    and cooling ramps.-   Polyisocyanate G aliphatic polyisocyanate based on allophanated HDI    trimer having an NCO % of 20 wt % based on ISO 11909:2007, a number    average functionality of 2.5 based on gel permeation chromatography,    and a Tg of 51° C. based on a Differential Scanning Calorimetry    reheat (2^(nd) Heating) from −100° C. to 150° C. using 20° C./min    heating and cooling ramps.-   Polyisocyanate H an aliphatic polyisocyanate based on HDI having an    NCO % of from 2%-5% based on ISO 11909:2007, a number average    functionality of 2 based on gel permeation chromatography, and a Tg    of 88° C. based on a Differential Scanning Calorimetry reheat    (2^(nd) Heating) from −100° C. to 150° C. using 20° C./min heating    and cooling ramps.

Various polyisocyanate resins were prepared for combination with apolyaspartate composition in an effort to achieve corrosion-resistantcoatings with stable gloss properties and good flexibility. Glossproperties were measured as a change in 60° gloss value over a period of4 weeks after application of the coating. Gloss values were measuredaccording to ASTM D523. Flexibility was measured at 4 weeks afterapplication of the coating via deformation resistance testing based onASTM D2794. 60° gloss values were determined under each of two separatesets of conditions. Standard conditions included storing the coating at75° F. and 55% relative humidity for a period of 4 weeks. Acceleratedconditions were performed at 80% relative humidity with an initialheating period of 120° F. for 30 minutes, followed by a subsequentstorage temperature of 104° F. for the remainder of the 4 weeks.Deformation resistance values were determined only under acceleratedconditions. Suitable coating compositions were considered to be thosethat achieved a change in 60° gloss value of less than or equal to 9gloss units under standard storage conditions, a change in 60° glossvalue of less than or equal to 20 gloss units under accelerated storageconditions, and deformation resistance values of greater than or equalto 30 inch-pounds under accelerated storage conditions.

The various example polyisocyanate resins were prepared usingPolyisocyanates A-H. Table 1 presents each of the example polyisocyanateresins and the corresponding weight percentages of Polyisocyanates A-Hthat were combined together to prepare the example polyisocyanateresins.

TABLE 1 Polyisocyanate Resins A B C D E F G H Resin ID % % % % % % % %Comparative Resin 1 100 Comparative Resin 2 60 40 Comparative Resin 3 8812 Comparative Resin 4 60 20 20 Comparative Resin 5 60 30 10 ComparativeResin 6 40 60 Comparative Resin 7 60 40 Comparative Resin 8 50 50Comparative Resin 9 40 60 Comparative Resin 10 60 40 Comparative Resin11 20 80 Comparative Resin 12 50 30 20 Comparative Resin 13 50 30 20Inventive Resin 1 40 40 20 Inventive Resin 2 40 40 20 Inventive Resin 330 40 30 Inventive Resin 4 30 40 30 Inventive Resin 5 30 50 20 InventiveResin 6 30 30 40 Inventive Resin 7 30 30 40 Inventive Resin 8 45 30 25Inventive Resin 9 45 30 25 Inventive Resin 10 47 34 19 Inventive Resin11 35 45 20 Inventive Resin 12 35 45 20 Inventive Resin 13 39 39 22

Each of the resins presented in Table 1 was combined with a 70:30 blendof Polyaspartate A:Polyaspartate B at an index of 1.05 NCO/NH to preparerespective coating compositions. For gloss measurements, the individualcoating compositions were applied to 4×8 inch sandblasted steel panelswith a 1-2 mil profile (SSPC SP-10) at a wet film thickness of 8-10mils. For impact resistance, the individual coating compositions wereapplied to 4×12 B952 P99X steel panels at a wet film thickness of 8-10mils. The coatings were then stored under the standard and acceleratedconditions described above. The 60° gloss values and deformationresistance values for coatings based on the individual resins describedabove are presented below in Table 2.

TABLE 2 Results Deformation Δ °60 Gloss Δ °60 Gloss Resistance Resin ID(Standard) (Accelerated) (In-Lbs) Comparative Resin 1 6.3 11 20Comparative Resin 2 4.9 6.7 25 Comparative Resin 3 9.8 18.3 30Comparative Resin 4 3.6 6.1 25 Comparative Resin 5 3.5 6.7 25Comparative Resin 6 22.3 25.9 160 Comparative Resin 7 24 26 140Comparative Resin 8 15.4 22.1 120 Comparative Resin 9 15.6 17.3 160Comparative Resin 10 12.8 22.6 60 Comparative Resin 11 5.8 25.3 55Comparative Resin 12 7.8 7.5 25 Comparative Resin 13 5.6 5.9 20Inventive Resin 1 4.6 15.6 40 Inventive Resin 2 7 9 30 Inventive Resin 38.9 19.2 55 Inventive Resin 4 9 15.2 60 Inventive Resin 5 8.6 10.5 55Inventive Resin 6 3.5 19 50 Inventive Resin 7 3.3 10.8 45 InventiveResin 8 3.8 5.6 30 Inventive Resin 9 0.6 4.9 30 Inventive Resin 10 3 4.830 Inventive Resin 11 4.3 8.3 35 Inventive Resin 12 7.1 16.3 35Inventive Resin 13 4.5 5.9 35

As can be seen from the results presented in Table 2, each of theinventive resins was suitable to prepare a coating having a change in60° gloss value of less than or equal to 9 gloss units under standardstorage conditions, a change in 60° gloss value of less than or equal to20 gloss units under accelerated storage conditions, and deformationresistance values of greater than or equal to 30 inch-pounds underaccelerated storage conditions. Further, in some cases, the inventiveexamples were able to exceed these threshold parameters by aconsiderable margin in at least one, if not all, categories.

In contrast, the comparative resins did not meet each of theseparameters. In some cases, one or more of the comparative examples wereable to achieve one or more suitable gloss parameters, but were not ableto achieve suitable deformation resistance values. In some other cases,one or more of the comparative examples were able to achieve suitabledeformation resistance values, but were not able to achieve one or moresuitable gloss parameters.

It should be understood that the above-described examples are onlyillustrative of some embodiments of the present invention. Numerousmodifications and alternative arrangements may be devised by thoseskilled in the art without departing from the spirit and scope of thepresent invention and the appended claims are intended to cover suchmodifications and arrangements. Thus, while the present invention hasbeen described above with particularity and detail in connection withwhat is presently deemed to be the most practical and preferredembodiments of the invention, it will be apparent to those of ordinaryskill in the art that variations including, may be made withoutdeparting from the principles and concepts set forth herein.

What is claimed is:
 1. A polyisocyanate resin, comprising: from 25 wt %to 50 wt %, based on a total weight of the polyisocyanate resin, of afirst cycloaliphatic polyisocyanate having an NCO % of from 12 wt % to20 wt % based on ISO 11909:2007; and from 50 wt % to 75 wt %, based on atotal weight of the polyisocyanate resin, of a flexibilizing component,comprising an isocyanate-terminated reaction product of a secondcycloaliphatic polyisocyanate and an isocyanate-reactive material, theisocyanate-terminated reaction product having a Tg of less than −30° C.based on a Differential Scanning Calorimetry (2^(nd) Heating)temperature scan from −100° C. to 150° C. using 20° C./min heating andcooling ramps, and a linear aliphatic polyisocyanate having a numberaverage isocyanate functionality of from 2 to 3 based on gel permeationchromatography, wherein the isocyanate-terminated reaction product andthe linear aliphatic polyisocyanate are present at a weight ratio offrom 0.5 to
 3. 2. The polyisocyanate resin of claim 1, wherein the firstcycloaliphatic polyisocyanate has a number average isocyanatefunctionality of from 2.4 to 3.8.
 3. The polyisocyanate resin of claim1, wherein the first cycloaliphatic polyisocyanate comprises an IPDIpolyisocyanate.
 4. The polyisocyanate resin of claim 3, wherein the IPDIpolyisocyanate comprises an IPDI trimer, an IPDI allophanate, or acombination thereof.
 5. The polyisocyanate resin of claim 1, wherein theisocyanate-terminated reaction product has a number average isocyanatefunctionality of from 1.8 to 2.8.
 6. The polyisocyanate resin of claim1, wherein the isocyanate-terminated reaction product has an NCO % offrom 2 wt % to 14 wt % based on ISO 11909:2007.
 7. The polyisocyanateresin of claim 1, wherein the second cycloaliphatic polyisocyanatecomprises an IPDI polyisocyanate.
 8. The polyisocyanate resin of claim7, wherein the IPDI polyisocyanate comprises an IPDI trimer, an IPDIallophanate, or a combination thereof.
 9. The polyisocyanate resin ofclaim 1, wherein the linear aliphatic polyisocyanate has an NCO % offrom 15 wt % to 25 wt % based on ISO 11909:2007.
 10. The polyisocyanateresin of claim 1, wherein linear aliphatic polyisocyanate comprises anHDI polyisocyanate, a PDI polyisocyanate, or a combination thereof. 11.The polyisocyanate resin of claim 1, wherein the linear aliphaticpolyisocyanate comprises an allophanate.
 12. The polyisocyanate resin ofclaim 1, wherein the polyisocyanate resin is diluted in a solvent toform a polyisocyanate composition having a total solids content of from80 wt % to 99 wt % based on a total weight of the polyisocyanatecomposition.
 13. The polyisocyanate resin of claim 12, wherein thesolvent comprises ethyl acetate, butyl acetate, 1-methoxypropyl-acetate-2, acetone, methyl ethyl ketone, methyl isobutyl ketone,cyclohexanone, toluene, xylene, solvent naphtha, or a combinationthereof.
 14. The polyisocyanate resin of claim 12, wherein thepolyisocyanate composition has a viscosity of from 500 mPas to 1300 mPasat 25° C. based on ISO 3219/A.3.
 15. The polyisocyanate resin of claim12, wherein the polyisocyanate composition has an NCO % of from 8 wt %to 16 wt % based on ISO 11909:2007.
 16. A coating composition,comprising: the polyisocyanate resin of claim 1; and a polyaspartatecomposition, wherein the polyisocyanate resin and the polyaspartatecomposition are combined at an NCO:NH equivalent ratio of from 1:1 to1.2:1.
 17. A polyurea coating, comprising: the coating composition ofclaim 16 applied to a surface portion of a substrate at a coatingthickness of from 1 mil to 16 mil.
 18. The polyurea coating of claim 17,wherein the polyurea coating has a change in 60° gloss value of lessthan 7 gloss units from 4 hours to 4 weeks after applying the coatingcomposition to the surface portion based on ASTM D523 and storageconditions of 75° F. and relative humidity of 55%.
 19. The polyureacoating of claim 17, wherein the polyurea coating has a deformationresistance of at least 30 inch-pounds 4 weeks after applying the coatingcomposition to the surface portion based on ASTM D2794 and initialstorage conditions at 120° F. for and 80% relative humidity for 30minutes and subsequent storage conditions of 104° F. and relativehumidity of 80%.
 20. A method of manufacturing a polyisocyanate resin,comprising: combining a first cycloaliphatic polyisocyanate having anNCO % of from 12 wt % to 20 wt % based on ISO 11909:2007 and aflexibilizing component at a weight ratio of from 0.3 to 1, wherein theflexibilizing component, comprises: an isocyanate-terminated reactionproduct of a second cycloaliphatic polyisocyanate and anisocyanate-reactive material, the reaction product having a Tg of lessthan −30° C. based on a Differential Scanning Calorimetry (2^(nd)Heating) temperature scan from −100° C. to 150° C. using 20° C./minheating and cooling ramps, and a linear aliphatic polyisocyanate havinga number average isocyanate functionality of from 2 to 3 based on gelpermeation chromatography, wherein the isocyanate-terminated reactionproduct and the linear aliphatic polyisocyanate are combined at a weightratio of from 0.5 to 3.